CN103044597B - A kind of propene polymer and preparation method thereof - Google Patents
A kind of propene polymer and preparation method thereof Download PDFInfo
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- CN103044597B CN103044597B CN201110309974.4A CN201110309974A CN103044597B CN 103044597 B CN103044597 B CN 103044597B CN 201110309974 A CN201110309974 A CN 201110309974A CN 103044597 B CN103044597 B CN 103044597B
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Abstract
The invention provides a kind of propene polymer and preparation method thereof, method of the present invention comprises: under the first alkene gas-phase polymerization condition, first part's propylene and first part hydrogen are carried out first contact, remove described first and contact unreacted monomer and hydrogen in the mixture obtained, obtain the first product of contact; Under the second alkene gas-phase polymerization condition, make described first product of contact carry out second with second section propylene, second section hydrogen and comonomer to contact, to obtain described propene polymer, described olefin polymerization catalyst system contains external donor compound, and described external donor compound contains the first external donor compound being selected from tetraethoxysilane and n-propyl Trimethoxy silane and the second external donor compound being selected from diisopropyl dimethoxy silane and second, isobutyl dimethoxy silane.Method hydrogen response of the present invention is good and polymerization efficiency is high.
Description
Technical field
The present invention relates to a kind of propene polymer and preparation method thereof.
Background technology
Polyacrylic production cost is low, good rigidly, and tool has been widely used.But alfon exists the shortcoming of toughness or shock resistance difference, need to carry out toughening modifying.Improving the toughness of alfon or a kind of conventional method of shock resistance is that propylene and ethene and/or alpha-olefin are carried out copolymerization, to introduce rubber phase in alfon, thus the propene polymer of acquisition is made to have good toughness or shock resistance.
While acquisition has the propene polymer of high toughness or shock resistance, also wish that propene polymer has good processibility.The Main Means improving the processibility of propene polymer improves its fluidity of molten, that is, improve the melt mass flow rate (MFR) of propene polymer.High fluidity propylene polymers can not only reduce the defect in injection technique, and then rate of reducing the number of rejects and seconds; But also processing temperature, injection pressure and mold clamping pressure etc. can be reduced, thus reduce energy consumption, shorten the shaping cycle of goods.Because the mobility of resin improves, can also thin-gage goods be produced, reduce raw-material usage quantity.In order to improve the melt mass flow rate of propene polymer, usually take following two kinds of modes of production :-kind be edman degradation Edman, another kind is that hydrogen adjusts method.Edman degradation Edman is in extruding pelletization process, in propene polymer, add organo-peroxide, and the macromolecular chain of propene polymer is ruptured, and then reduces the melt viscosity of propene polymer, the melt mass flow rate of corresponding raising propene polymer.But the propene polymer prepared by the method easily turns to be yellow, and with certain smell.
Hydrogen tune method is the density of hydrogen by improving in the course of the polymerization process in polymeric kettle, impels the macromolecular chain generation chain tra nsfer of propene polymer, reduces the molecular-weight average of propene polymer, thus the propene polymer of acquisition high workability.The yellowness index of the propene polymer adopting hydrogen to adjust legal system standby is low, appearance stablity; Volatile content in product is low, can be used in the occasion that automotive upholstery etc. has higher requirements to smell.
But in actual mechanical process, when amounts of hydrogen increases to a certain degree, the degree that the melt mass flow rate of propene polymer increases reduces, and also makes the activity decrease of catalyzer, affects polymerization efficiency simultaneously.In addition, the increase of hydrogen usage is also had higher requirement to the pressure control capability of polymerization reactor, the ability of removing heat energy power and bearing high-load.
Therefore, when adopting hydrogen to adjust method to regulate the melt mass flow rate of propene polymer, the hydrogen response (that is, the melting index of polymkeric substance is with the intensity of variation of the add-on of hydrogen) improving the olefin polymerization catalyst system used is crucial.
US5652303, US5844046, US6111039 and US6087459 individually disclose propylene when being polymerized in the liquid phase, two kinds of silane compounds can be used as external donor compound, improve the hydrogen response of Ziegler-Natta catalyst, thus improve the melt mass flow rate of the propene polymer of preparation.Although in alkene (particularly propylene) polymerization process, adopt external donor compound disclosed in US5652303, US5844046, US6111039 and US6087459, the melt mass flow rate of the polymkeric substance finally obtained can be improved to a certain extent, but the hydrogen response of above-mentioned olefin polymerization catalyst system still awaits further raising.Further, above-mentioned two kinds of silane compounds are used still to be difficult to obtain balance between good hydrogen response and high catalytic activity as the olefin polymerization catalyst system of external donor compound.In addition, adopt external donor compound disclosed in US5652303, US5844046, US6111039 and US6087459, when preparing propene polymer in the mode of vapour phase polymerization, very difficult acquisition has the propene polymer of high melt mass flow index.
To sum up, a kind of gas phase polymerization process that can have a propene polymer of high melt mass flow rate with higher polymerization efficiency and the preparation of lower hydrogen usage is provided to remain a technical problem urgently to be resolved hurrily.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of propene polymer, the method can obtain good balance between hydrogen response and polymerization efficiency, can have the propene polymer of high melt mass flow rate with the preparation of higher polymerization efficiency.
The invention provides a kind of preparation method of propene polymer, the method comprises:
Under the first alkene gas-phase polymerization condition, first part's propylene and first part hydrogen are carried out first and contacts, remove described first and contact unreacted monomer and hydrogen in the mixture obtained, obtain the first product of contact; And
Under the second alkene gas-phase polymerization condition, make described first product of contact carry out second with second section propylene, second section hydrogen and comonomer and contact, to obtain described propene polymer, described comonomer is for being selected from ethene, C
4-C
101-alkene and C
4-C
8diolefin in one or more alkene;
Wherein, described first contact is carried out under the existence of olefin polymerization catalyst system, described olefin polymerization catalyst system contains solid ingredient, external donor compound and organo-aluminium compound, described solid ingredient contains titanium, magnesium and internal electron donor compound, described external donor compound contains the first outer Donor compound and the second external donor compound, described first external donor compound is tetraethoxysilane and/or n-propyl Trimethoxy silane, described second external donor compound is diisopropyl dimethoxy silane and/or second, isobutyl dimethoxy silane.
Invention further provides a kind of propene polymer prepared by method of the present invention.
According to the preparation method of propene polymer of the present invention, in the olefin polymerization catalyst system used, described external donor compound comprises one or both the first external donor compound be selected from tetraethoxysilane and n-propyl Trimethoxy silane and one or both the second external donor compound be selected from diisopropyl dimethoxy silane and second, isobutyl dimethoxy silane; And described first external donor compound and described second external donor compound are sent in described first gas-phase polymerization reactor, make described first part propylene and hydrogen carry out first contacts and carries out under the existence of described first external donor compound and described second external donor compound all the time simultaneously.
Only carry out under the existence of described first external donor compound or described second external donor compound with the contact of described first part propylene and hydrogen, or first make the contact of described first part propylene and hydrogen carry out under the existence of described first external donor compound, the mode that the mixture obtained carries out further being polymerized again under the existence of described second external donor compound is compared, and can not only prepare the propene polymer with higher melt mass flow rate according to method of the present invention; But also there is higher polymerization efficiency.In addition, prepared according to the methods of the invention propene polymer also has higher degree of isotacticity.
Such as: according to method of the present invention, when described comonomer is ethene, only make in the first contact, the mol ratio of hydrogen and first part's propylene is 0.075-0.095: 1, in second contact, the mol ratio of hydrogen and second section propylene is 0.018-0.028: 1, and the melt mass flow rate of the propene polymer of preparation just can reach 80 grams/more than 10 minutes, within the scope being generally in 80-150 gram/10 minutes; And the degree of isotacticity of propene polymer of preparation can reach more than 95%, within the scope being generally in 95-98%.
In addition, method according to the present invention is easy and simple to handle, and can implement without the need to carrying out transformation to existing gas-phase polymerization reactor.
Embodiment
The invention provides a kind of preparation method of propene polymer, the method comprises: under the first alkene gas-phase polymerization condition, first part's propylene and first part hydrogen are carried out first contact, remove described first and contact unreacted monomer and hydrogen in the mixture obtained, obtain the first product of contact.
According to method of the present invention, described first contact is carried out under the existence of olefin polymerization catalyst system.In the present invention, " described first contact carry out under the existence of olefin polymerization catalyst system " refers to that described first part propylene contacts with the mixture of each component in described olefin polymerization catalyst system with first part hydrogen, is polymerized to make propylene.
In actual mechanical process, described first contact is carried out realizing in the following manner under the existence of olefin polymerization catalyst system: sent into by olefin polymerization catalyst system in gas-phase polymerization reactor, mix, then first part's propylene and first part hydrogen are sent in gas-phase polymerization reactor, and described first part propylene is contacted with the mixture of each component in described olefin polymerization catalyst system with first part hydrogen.Particularly, described first contacts the implementation of carrying out under the existence of olefin polymerization catalyst system can be: the solid ingredient in described olefin polymerization catalyst system and organo-aluminium compound are sent in the first gas-phase polymerization reactor, then external donor compound (comprising the first external donor compound and the second external donor compound) is sent in described first gas-phase polymerization reactor and mix with described solid ingredient and organo-aluminium compound, then described first part propylene is sent in described first gas-phase polymerization reactor with first part hydrogen and contact with the mixture of each component in olefin polymerization catalyst system, to be polymerized under olefinic polyreaction condition.
According to method of the present invention, described olefin polymerization catalyst system contains external donor compound.In the present invention, described external donor compound is the first external donor compound and the second external donor compound (that is, described external donor compound is the mixture of the first external donor compound and the second external donor compound).According to the present invention, described first external donor compound is tetraethoxysilane and/or n-propyl Trimethoxy silane, and described second external donor compound is diisopropyl dimethoxy silane and/or second, isobutyl dimethoxy silane.From the angle improved further according to method hydrogen response of the present invention and polymerization efficiency, described first external donor compound is tetraethoxysilane, and described second external donor compound is diisopropyl dimethoxy silane or second, isobutyl dimethoxy silane; Or described first external donor compound is n-propyl Trimethoxy silane, described second external donor compound is second, isobutyl dimethoxy silane.
As mentioned before, according to method of the present invention, described first contact is carried out under the existence of olefin polymerization catalyst system.Therefore, described first external donor compound and described second external donor compound should be sent into the same position in described first gas-phase polymerization reactor simultaneously and mix, to contact with hydrogen with described first part propylene.In actual mechanical process, described first external donor compound and described second external donor compound can be added in gas-phase polymerization reactor by one or more charging opening simultaneously, described multiple charging opening along described first gas-phase polymerization reactor circumference arrange and identical in the position axially of described first gas-phase polymerization reactor, carry out under the existence of olefin polymerization catalyst system with the contact realizing described first part propylene and first part's hydrogen.According to the present invention, the position of described charging opening can be the routine selection of this area, is not particularly limited.
The present inventor finds in research process: with the first external donor compound and the second external donor compound are successively sent in described first reactor, the contact of first part's propylene and first part's hydrogen is first carried out under the existence of the first external donor compound, then compared with mixture contact obtained carries out contact again with the second external donor compound, the propene polymer with higher melt mass flow index can not only be obtained according to method of the present invention, but also high polymerization efficiency can be obtained (namely, use the olefin polymerization catalyst system of equal in quality can obtain more polymkeric substance, also namely, olefin polymerization catalyst system is made to have high catalytic activity), the propene polymer simultaneously obtained also has high degree of isotacticity (generally can reach more than 95%).
According to method of the present invention, the mol ratio of described first external donor compound and described second external donor compound can change in wide in range scope.Preferably, the mol ratio of described first external donor compound and described second external donor compound is for being more than or equal to 0.5: 1.More preferably, the mol ratio of described first external donor compound and the second external donor compound is 1-199: 1.Under guaranteeing that the propene polymer prepared has the prerequisite of high melt mass flow rate, there is the angle of higher degree of isotacticity, the mol ratio of described first external donor compound and described second external donor compound more preferably 1-99: 1 from the propene polymer improving further polymerization efficiency and preparation.
Most preferably, the mol ratio of described first external donor compound and described second external donor compound is 9-39: 1.When the mol ratio of described first external donor compound and described second external donor compound is 9-39: 1, on the one hand there is more excellent hydrogen response according to method according to the present invention; According to method of the present invention, also there is higher polymerization efficiency on the other hand, and the propene polymer of preparation also has higher degree of isotacticity.
According to method of the present invention, described olefin polymerization catalyst system is also containing solid ingredient and organo-aluminium compound, and described solid ingredient contains titanium, magnesium and internal electron donor compound.The present invention is not particularly limited for described solid ingredient and organo-aluminium compound, can be that the routine of this area is selected.
According to the present invention, the various solid ingredients that described solid ingredient can be commonly used for Ziegler-natta catalyst.Usually, described solid ingredient contains titanium, magnesium and internal electron donor compound, is the reaction product of titanium compound, magnesium compound and internal electron donor compound.
According to the present invention, described titanium compound can be various titanium compounds conventional in Ziegler-natta catalyst.Preferably, described titanium compound is the titanium compound shown in formula I,
TiX
1 m(OR
1)
4-m(I)
In formula I, X
1can be the one in chlorine, bromine and iodine, R
1can be C
1-C
5straight or branched alkyl, m can be the integer of 0-4.In formula I, m can be such as 0,1,2,3 or 4.
In the present invention, C
1-C
5straight or branched alkyl example can for but be not limited to: methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl, n-pentyl, isopentyl, tert-pentyl and neo-pentyl.
In the present invention, the example of described titanium compound can for but be not limited to: one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, four titanium butoxide, purity titanium tetraethoxide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium and trichlorine one ethanolato-titanium.
Preferably, in formula I, X
1for the one in chlorine, bromine and iodine, R
1for C
1-C
5alkyl, m is the integer of 1-4, such as: described titanium compound can be one or more in titanium tetrachloride, titanium tetrabromide, titanium tetra iodide, a chlorine triethoxy titanium, dichlorodiethyl oxygen base titanium and trichlorine one ethanolato-titanium.
Further preferably, in formula I, m is 4, such as: described titanium compound can be one or more in titanium tetrachloride, titanium tetrabromide and titanium tetra iodide.Most preferably, in formula I, m is 4, and X
1for chlorine, namely described titanium compound is titanium tetrachloride.
According to the present invention, described magnesium compound can be the magnesium compound shown in formula II,
R
3-Mg-R
2(II)
In formula II, R
2and R
3can be chlorine, bromine, iodine, C separately
1-C
5straight or branched alkoxyl group and C
1-C
5straight or branched alkyl in one.In the present invention, C
1-C
5straight or branched alkoxyl group include but not limited to: methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy, n-pentyloxy, isopentyloxy, tertiary pentyloxy and neopentyl oxygen.
Preferably, in formula II, R
2and R
3be the one in chlorine, bromine and iodine separately.Most preferably, in formula II, R
2and R
3be chlorine, namely described magnesium compound is magnesium dichloride.
According to the present invention, described internal electron donor compound can be the conventional various internal electron donor compound of field of olefin polymerisation, such as: described internal electron donor compound can be one or more in bialkyl ortho phthalate based compound.Preferably, described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate.
One of the present invention preferred embodiment in, in formula I, X
1for the one in chlorine, bromine and iodine, m is 4; And in formula II, R
2and R
3be separately the one in chlorine, bromine and iodine, described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate.
One of the present invention more preferred embodiment in, described titanium compound is titanium tetrachloride; Described magnesium compound is magnesium chloride; And described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate.
According to the present invention, can adopt and well known to a person skilled in the art that various method prepares described solid ingredient.Such as, the preparation method of described solid ingredient can comprise: contacted in organic solvent with internal electron donor compound with titanium compound by described magnesium compound, then carries out solid-liquid separation, and carries out washing and drying.According to the present invention, the consumption of described titanium compound, internal electron donor compound and magnesium compound is with in final solid ingredient, and the content of each component meets concrete service requirements and is as the criterion.Preferably, the mol ratio of described titanium compound, internal electron donor compound and magnesium compound is 0.01-0.5: 0.01-50: 1.
According to method of the present invention, the preparation method of described solid ingredient is preferably: under the existence of hydrocarbon system solvent, at the temperature of 110-150 DEG C, described magnesium compound is contacted 1-3 hour with alcohol; Again at the temperature of 110-150 DEG C, product of contact is contacted with the first internal electron donor compound with titanic acid ester, thus prepares alcohol adduct; At the temperature of-10 DEG C to-30 DEG C, titanium compound is dripped in described alcohol adduct, after being added dropwise to complete, the temperature of the mixture obtained is increased to 100-130 DEG C, and at such a temperature, the second internal electron donor compound is added in described mixture, then at the temperature of 100-130 DEG C, contact 1-3 hour, product of contact is filtered, washed and carry out drying, described solid ingredient can be obtained.Described first internal electron donor compound and described second internal electron donor compound can be previously described internal electron donor compound separately.Described first internal electron donor compound can be identical with described second internal electron donor compound, also can be different, preferably identical.The mol ratio of described first internal electron donor compound and described magnesium compound can be 0.1-0.2: 1.The mol ratio of described titanium compound, the second internal electron donor compound and magnesium compound can be 0.01-0.5: 0.01-50: 1.Described hydrocarbon system solvent can be C
6-C
10straight or branched hydrocarbon, described titanic acid ester can be such as one or more in titanium isopropylate, tetra-n-butyl titanate and tetraethyl titanate.The mol ratio of described titanic acid ester and described magnesium compound can be 0.05-0.1: 1.
According to the present invention, the various organo-aluminium compounds that described organo-aluminium compound can be commonly used for this area.Usually, described organo-aluminium compound can be one or more in the organo-aluminium compound shown in formula III,
Wherein, R
4, R
5and R
6can be chlorine and C separately
1-C
5straight or branched alkyl in one, and R
4, R
5and R
6in at least one is C
1-C
5straight or branched alkyl.
Preferably, described organo-aluminium compound is one or more in trimethyl aluminium, triethyl aluminum, triisobutyl aluminium and diethyl aluminum chloride.Further preferably, described organo-aluminium compound is triethyl aluminum.
One of the present invention preferred embodiment in, described titanium compound is titanium dichloride; Described magnesium compound is magnesium chloride; Described internal electron donor compound is one or more in diisobutyl phthalate, n-butyl phthalate, n-propyl phthalate, diisopropyl phthalate, diethyl phthalate and dimethyl phthalate; And described organo-aluminium compound is triethyl aluminum.
According to method of the present invention, the amount of the solid ingredient in described olefin polymerization catalyst system, external donor compound and organo-aluminium compound can carry out appropriate selection according to concrete application scenario.Usually, the mol ratio of the titanium in the aluminium in described organo-aluminium compound and described solid ingredient can be 20-2000: 1, is preferably 50-1000: 1, more preferably 200-800: 1; The mol ratio of silicon total in the aluminium in described organo-aluminium compound and described external donor compound can be 1-100: 1, is preferably 5-80: 1, more preferably 20-80: 1.
Also comprising according to method of the present invention to contact after the mixture obtained removes unreacted monomer and hydrogen by first, obtain the first product of contact; Under the second alkene gas-phase polymerization condition, make described first product of contact carry out second with second section propylene, second section hydrogen and comonomer and contact, to obtain described propene polymer.
The various methods that this area can be adopted to commonly use remove unreacted monomer and hydrogen in the mixture that the first contact obtains, and repeat no more herein.
According to method of the present invention, the described first ratio of amount in the propene polymer finally obtained contacting the product obtained can carry out appropriate selection according to the expection application scenario of the propene polymer finally obtained.Usually, with the total amount of described propene polymer for benchmark, the massfraction of described first product of contact can be 40-99.5%, is preferably 50-98%, is more preferably 50-96%.
In the present invention, described comonomer can carry out the olefinic monomer of copolymerization with propylene for various.Preferably, described comonomer is for being selected from ethene, C
4-C
101-alkene and C
4-C
8diolefin in one or more alkene.In the present invention, described C
4-C
101-alkene specific examples can for but be not limited to: the positive amylene of 1-n-butene, 1-, 1-n-hexylene, the positive octene of 1-and 4-methyl-1-pentene; Described C
4-C
8diolefin example can for but be not limited to: 1,3-butadiene and isoprene.
Method according to the present invention is particularly useful for making ethylene-propylene copolymer, and therefore described comonomer is particularly preferably ethene.
According to method of the present invention, the consumption of described comonomer can carry out appropriate selection according to the final occasion of the propene polymer finally obtained, and is as the criterion with the requirement making the performance of the propene polymer finally obtained meet expection.Usually, have higher toughness or the angle of shock resistance from the propene polymer making finally to obtain, the mol ratio of described comonomer and described second section propylene is preferably 0.01-2: 1.
According to method of the present invention, hydrogen adds in polymerization system as molecular weight regulator.The consumption of hydrogen can be adjusted according to the melt mass flow rate of predetermined propene polymer.Method according to the present invention has high hydrogen response, therefore only uses a small amount of hydrogen (that is, under low-hydrogen density) can prepare the propene polymer with high melt mass flow rate.Such as, when to prepare melt mass flow rate adopting method of the present invention be the multipolymer of the propylene of 80-150 gram/10 minutes and ethene, in described first contact, the mol ratio of described first part hydrogen and described first part propylene can be only 0.075-0.095: 1; In described second contact, the mol ratio of described second section hydrogen and described second section propylene can be only 0.018-0.028: 1.
In the present invention, described melt mass flow rate is the method according to specifying in GB/T 3682-2000, at the temperature of 230 DEG C, measures when load is 2.16 kilograms.
One of the present invention preferred embodiment in, using ethene as comonomer; With the total amount of the propene polymer finally obtained for benchmark, the massfraction of the product of described first contact is 40-99.5%; The mol ratio of described comonomer and described second section propylene is 0.01-2: 1; And in described first contact, the mol ratio of described first part hydrogen and described first part propylene is 0.075-0.095: 1; In described second contact, the mol ratio of described second section hydrogen and described second section propylene is 0.018-0.028: 1, the ethylene-propylene polymer of preparation like this not only has excellent toughness, and there is high melt mass flow rate and degree of isotacticity, can use as high-impact propene polymer.
According to method of the present invention, described first alkene gas-phase polymerization condition and described second alkene gas-phase polymerization condition can be the normal condition of this area.Usually, described first alkene gas-phase polymerization condition comprises: temperature can be 40-90 DEG C, and pressure can be 0.5-4MPa; Described second alkene gas-phase polymerization condition comprises: temperature can be 40-90 DEG C, and pressure can be 0.5-4MPa.
According to method of the present invention, described first contact to contact the reactor (such as: in fluidized-bed reactor and horizontal type agitated bed gas-phase polymerization reactor) that can realize the vapour phase polymerization of alkene can commonly used in this area separately and carries out with described second.Olefine polymerizing process according to the present invention is particularly suitable for carrying out in horizontal type agitated bed gas-phase polymerization reactor, to produce granulated polymer.
According to method of the present invention, described first contact contacts can carry out in a reactor with described second, also can carry out in the reactor of two series connection.Carry out in two reactors improving the production efficiency according to method of the present invention further.
One according to the present invention preferred embodiment in, described first contact and described second contacts in the gas-phase polymerization reactor be connected in series at two and carries out, and using ethene as comonomer, the preparation method of described propene polymer comprises:
Under the first alkene gas-phase polymerization condition, first part's propylene and first part hydrogen are carried out first with olefin polymerization catalyst system in first gas-phase polymerization reactor and contacts; And
Send in second gas-phase polymerization reactor after the mixture obtained after described first contact is removed unreacted monomer and hydrogen, under the second alkene gas-phase polymerization condition, make described first product of contact carry out second with second section propylene, ethene and second section hydrogen and contact;
Wherein, with the total amount of described propene polymer for benchmark, the massfraction of described first product of contact is 40-99.5%, and the mol ratio of described comonomer and described second section propylene is 0.01-2: 1.
Present invention also offers a kind of propene polymer prepared by method of the present invention.
Prepared according to the methods of the invention propene polymer has high melt mass flow rate.Particularly, when using ethene as comonomer, the melt mass flow rate of described propene polymer can reach 80 grams/more than 10 minutes, within the scope being generally in 80-150 gram/10 minutes.
Prepared according to the methods of the invention propene polymer also has high degree of isotacticity.Particularly, when using ethene as comonomer, the degree of isotacticity according to propene polymer of the present invention can reach more than 95%, within the scope being generally in 95-98%.
According to propene polymer of the present invention, when described alkene is ethene, the ethylene-propylene polymer adopting method of the present invention to prepare has high toughness (that is, high shock resistance).
The present invention is described in detail below in conjunction with embodiment.
The testing method related in following examples is as follows.
(1) melt mass flow rate: according to the testing method specified in GB/T 3682-2000, carries out being purchased on the TP402-2 type melt mass flow rate determinator of Japanese Tester company.Wherein, probe temperature is 230 DEG C, and load is 2.16 kilograms.
(2) ethylene content: adopt infrared spectroscopy, sample pellet is hot pressed into the film that thickness is 200-400 micron on the thermocompressor of 160 DEG C, after naturally cooling to room temperature, tests being purchased on the IR-435 infrared spectrometer of Japanese Shimadzu.
(3) rubber-phase content in propene polymer: adopt n-decane extraction process, concrete operations are: the n-decane being 98 % by weight by propene polymer and purity mixes (weight ratio of the two is 1: 10), in 145 DEG C of backflows 24 hours in the flask with reflux, then room temperature is cooled to, rubber compatibility in propene polymer is in decane, all the other crystallize out, then filter, and by filtrate added drop-wise in acetone, rubber phase in filtrate is separated out, after filtration, after drying, weigh, determine the content of rubber phase.
(4) degree of isotacticity: adopt
13c-NMR, according to scholar's Xiao mirror and the raw work of remaining tax " Catalysts for Olefin Polymerization and polyolefine " (press of Beijing University of Technology, 2002) method disclosed in the 266th page, the percentage composition calculating polypropylene five unit group [mmmm] obtains degree of isotacticity.Wherein, carbon-13 nmr spectra detects and carries out in the AM300 NMR spectrometer with superconducting magnet of Switzerland Bruker being purchased, concrete operations condition is: dissolved with deuterated orthodichlorobenzene when temperature is 120 DEG C by sample, be mixed with the solution that concentration is 15 volume %, in the oil bath of 120 DEG C, dissolve 4-5 hour.
(5) molecular weight and molecualr weight distribution: adopt gel permeation chromatography, carry out on the WATER GPCV2K gel chromatograph of WATERS company being purchased, the moving phase used is orthodichlorobenzene, and probe temperature is 150 DEG C, adopts monodisperse polystyrene as standard substance.
(6) polymerization efficiency: refer in the unit time, by the quality of the polymkeric substance of the catalyst preparing of unit mass, calculation formula is: quality/(quality of polymerization reaction time × catalyzer) of the polymkeric substance of preparation, wherein, the quality of polymkeric substance in kilogram, the quality of catalyzer in gram, polymerization reaction time in hour.
Preparation example 1-4 is for the preparation of the solid ingredient in olefin polymerization catalyst system.
Preparation example 1
(1) preparation of magnesium chloride alcohol adduct
The there-necked flask nitrogen replacement three times of agitator and thermometer is housed, then adds 5g Magnesium Chloride Anhydrous, 30mL n-decane and 23mL ethanol.Warming while stirring to 130 DEG C, and react 2 hours at this temperature, in advance 1.5mL tetrabutyl titanate and 2mL diisobutyl phthalate are added in 5mL toluene, at room temperature stirring reaction 0.5 hour.Above-mentioned toluene solution is added in above-mentioned there-necked flask, and continues reaction 1 hour at 130 DEG C, after reaction terminates, be cooled to the magnesium chloride alcohol adduct solution that room temperature forms stable and uniform.
(2) preparation of catalyst solid constituent
The there-necked flask nitrogen replacement three times of agitator and thermometer is housed, and then add 200mL titanium tetrachloride, at-20 DEG C, magnesium chloride alcohol adduct solution step (1) prepared was added drop-wise in this reactor in 30 minutes.After being added dropwise to complete, be warming up to 110 DEG C through 3.5 hours.At 110 DEG C, add 1.2mL diisobutyl phthalate, and react 2 hours at this temperature.Reaction terminates rear filtering reaction solution, is washed 60 minutes by the solid trichloromethane obtained at 60 DEG C, and be then washed till without free chlorion in filtrate with hexane, remaining solid product obtains the solid ingredient of catalyzer through vacuum-drying.In this solid ingredient, the content of Ti is 2.36wt%.
Preparation example 2
(1) preparation of magnesium chloride alcohol adduct
The method identical with the step (1) in preparation example 1 is adopted to prepare magnesium chloride alcohol adduct, unlike, use n-butyl phthalate to replace diisobutyl phthalate, thus prepare magnesium chloride alcohol adduct solution.
(2) preparation of catalyst solid constituent
Adopt the solid ingredient of the method Kaolinite Preparation of Catalyst identical with the step (2) in preparation example 1, unlike, use n-butyl phthalate to replace diisobutyl phthalate, thus obtain the solid ingredient of catalyzer.In this solid ingredient, the content of Ti is 2.12wt%.
Preparation example 3
(1) preparation of magnesium chloride alcohol adduct
The method identical with the step (1) in preparation example 1 is adopted to prepare magnesium chloride alcohol adduct, unlike, use n-propyl phthalate to replace diisobutyl phthalate, thus prepare magnesium chloride alcohol adduct solution.
(2) preparation of catalyst solid constituent
Adopt the solid ingredient of the method Kaolinite Preparation of Catalyst identical with the step (2) in preparation example 1, unlike, use n-propyl phthalate to replace diisobutyl phthalate, thus obtain the solid ingredient of catalyzer.In this solid ingredient, the content of Ti is 2.03wt%.
Preparation example 4
(1) preparation of magnesium chloride alcohol adduct
The method identical with the step (1) in preparation example 1 is adopted to prepare magnesium chloride alcohol adduct, unlike, use diisopropyl phthalate to replace diisobutyl phthalate, thus prepare magnesium chloride alcohol adduct solution.
(2) preparation of catalyst solid constituent
Adopt the solid ingredient of the method Kaolinite Preparation of Catalyst identical with the step (2) in preparation example 1, unlike, use diisopropyl phthalate to replace diisobutyl phthalate, thus obtain the solid ingredient of catalyzer.In this solid ingredient, the content of Ti is 1.98wt%.
Embodiment 1-34 is used for illustrating according to propene polymer of the present invention and preparation method thereof.
Embodiment 1
Catalyst solid constituent preparation example 1 prepared joins first 50m continuously with 1.5g/h
3continuous horizontal type agitated bed Gas-phase reactor (hereinafter referred to as the first reactor) in, triethyl aluminum is added continuously with pump, the add-on of triethyl aluminum makes the mol ratio Al/Ti=400 of the aluminium in triethyl aluminum and the titanium in catalyst solid constituent, add the mixture (both mol ratios are DT/DP=39/1, the mol ratio Al/Si=20 of the total amount of the silicon in triethyl aluminum in the amount of aluminium and diisopropyl dimethoxy silane and tetraethoxysilane) of diisopropyl dimethoxy silane (DP) and tetraethoxysilane (DT) continuously.Then, in the first reactor, pass into propylene and hydrogen carries out polyreaction, wherein, the pressure of the first reactor is 2.20MPa, and the temperature of the first reactor is 64 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.1 (mol/mol), propylene and hydrogen mean residence time is in the reactor 40min, and the product obtained is delivered to second 50m after sending into and removing unreacted propylene and hydrogen in tundish by the mixture exported by the first reactor
3continuous horizontal type agitated bed Gas-phase reactor (hereinafter referred to as the second reactor), and in the second reactor, pass into the gas mixture of ethene and propylene, wherein, the pressure of the second reactor is 2.20MPa, the temperature of the second reactor is 65 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.05 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 0.3 (mol/mol), mean residence time is 40min.
Embodiment 2
The method identical with embodiment 1 is adopted to prepare propene polymer, unlike, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.075 (mol/mol), the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.025 (mol/mol).
Embodiment 3
The method identical with embodiment 2 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and diisopropyl dimethoxy silane is DT/DP=19/1, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.082 (mol/mol), the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.018 (mol/mol).
Embodiment 4
The method identical with embodiment 2 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and diisopropyl dimethoxy silane is DT/DP=12/1, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.095 (mol/mol), the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.026 (mol/mol).
Embodiment 5
The method identical with embodiment 4 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and diisopropyl dimethoxy silane is DT/DP=9/1.
Embodiment 6
The method identical with embodiment 2 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and diisopropyl dimethoxy silane is DT/DP=99/1.
Embodiment 7
The method identical with embodiment 4 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and diisopropyl dimethoxy silane is DT/DP=1/1.
Comparative example 1
The method identical with embodiment 2 is adopted to prepare propene polymer, unlike, do not use diisopropyl dimethoxy silane, and the add-on of tetraethoxysilane makes the mol ratio Al/Si=20 of the silicon in the amount of aluminium in triethyl aluminum and tetraethoxysilane.
Comparative example 2
The method identical with embodiment 2 is adopted to prepare propene polymer, unlike, do not use tetraethoxysilane, and the add-on of diisopropyl dimethoxy silane makes the mol ratio Al/Si=20 of the silicon in the amount of aluminium in triethyl aluminum and diisopropyl dimethoxy silane.
Embodiment 8
The method identical with embodiment 2 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and diisopropyl dimethoxy silane is DT/DP=199/1.
Embodiment 9
The method identical with embodiment 4 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and diisopropyl dimethoxy silane is DT/DP=0.67/1.
Comparative example 3
The method identical with embodiment 5 is adopted to prepare propene polymer, unlike, replace tetraethoxysilane and diisopropyl dimethoxy silane with four butoxy silanes and dimethoxydiphenylsilane, and the mol ratio of four butoxy silanes and dimethoxydiphenylsilane is 9/1.
Comparative example 4
The method identical with embodiment 5 is adopted to prepare propene polymer, unlike, replace tetraethoxysilane and diisopropyl dimethoxy silane with tetramethoxy-silicane and Cyclohexylmethyldimethoxysilane, and the mol ratio of tetramethoxy-silicane and Cyclohexylmethyldimethoxysilane is 9/1.
Comparative example 5
The method identical with embodiment 5 is adopted to prepare propene polymer, unlike, in the first reactor, the embodiment of polyreaction is:
Tetraethoxysilane and diisopropyl dimethoxy silane are successively sent into the first reactor from two charging openings, wherein, first charging opening and second charging opening are arranged along the axis of reactor, be benchmark along the travel direction of material in described first reactor, the distance that first charging opening is positioned at the initiating terminal of described first reactor is 8% place of the total length of described first reactor, and described first charging opening is for adding tetraethoxysilane; The distance that described second charging opening is positioned at the initiating terminal of described first reactor is 75% of the total length of described first reactor, and described second charging opening is for adding diisopropyl dimethoxy silane;
During polymerization, catalyst solid constituent and triethyl aluminum are sent into described first reactor from first charging opening respectively, and mixes with tetraethoxysilane, then pass into propylene and hydrogen from first charging opening, contact with said mixture and be polymerized; Be polymerized the mixture obtained then to contact with diisopropyl dimethoxy silane, proceed polymerization, and remove unreacted propylene and hydrogen in mixture feeding tundish polymerization obtained.
Embodiment 10
Catalyst solid constituent preparation example 2 prepared joins first 50m continuously with 1.5g/h
3continuous horizontal type agitated bed Gas-phase reactor (hereinafter referred to as the first reactor) in, triethyl aluminum is added continuously with pump, the add-on of triethyl aluminum makes the mol ratio Al/Ti=600 of the aluminium in triethyl aluminum and the titanium in catalyst solid constituent, add the mixture (both mol ratios are DT/DP=19/1, the mol ratio Al/Si=40 of the total amount of the silicon in triethyl aluminum in the amount of aluminium and diisopropyl dimethoxy silane and tetraethoxysilane) of diisopropyl dimethoxy silane and tetraethoxysilane continuously.Then, in the first reactor, pass into propylene and hydrogen carries out polyreaction, wherein, the pressure of the first reactor is 1.12MPa, and the temperature of the first reactor is 75 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.08 (mol/mol), propylene and hydrogen mean residence time is in the reactor 40min, and the product obtained is delivered to second 50m after sending into and removing unreacted propylene and hydrogen in tundish by the mixture exported by the first reactor
3continuous horizontal type agitated bed Gas-phase reactor (hereinafter referred to as the second reactor), and in the second reactor, pass into the gas mixture of ethene and propylene, wherein, the pressure of the second reactor is 1.12MPa, the temperature of the second reactor is 65 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.027 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 0.6 (mol/mol), mean residence time is 40min.
Table 1 lists the test result of embodiment 1-10 and comparative example 1-5.
Table 1
*: four butoxy silanes/dimethoxydiphenylsilane
*: tetramethoxy-silicane/Cyclohexylmethyldimethoxysilane
Embodiment 11
Catalyst solid constituent prepared by preparation example 2 is added 50m continuously with 1.5g/h
3continuous horizontal type agitated bed Gas-phase reactor in, triethyl aluminum is added continuously with pump, the add-on of triethyl aluminum makes the mol ratio Al/Ti=600 of the aluminium in triethyl aluminum and the titanium in catalyst solid constituent, add tetraethoxysilane and second, isobutyl dimethoxy silane (DB) (both molar ratios are DT: DB=39: 1, the total amount mol ratio Al/Si=20 of the silicon in triethyl aluminum in the amount of aluminium and tetraethoxysilane and second, isobutyl dimethoxy silane) continuously.Then, in the first reactor, pass into propylene and hydrogen carries out polyreaction, wherein, the pressure of the first reactor is 2.20MPa, and the temperature of the first reactor is 64 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.07 (mol/mol), propylene and hydrogen mean residence time is in the reactor 40min.After the mixture exported by first reactor is sent into and is removed unreacted propylene and hydrogen in tundish, the product obtained is delivered to the second reactor, and ethene is passed in the second reactor, the pressure of the second reactor is 2.20MPa, the temperature of the second reactor is 65 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.05 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 0.3 (mol/mol), mean residence time is 40min.
Embodiment 12
The method identical with embodiment 11 is adopted to prepare propene polymer, unlike, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.084 (mol/mol), the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.028 (mol/mol).
Embodiment 13
The method identical with embodiment 12 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and second, isobutyl dimethoxy silane is DT: DB=19: 1.
Embodiment 14
The method identical with embodiment 12 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and second, isobutyl dimethoxy silane is DT: DB=12: 1.
Embodiment 15
The method identical with embodiment 12 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and second, isobutyl dimethoxy silane is DT: DB=9: 1.
Embodiment 16
The method identical with embodiment 13 is adopted to prepare propene polymer, unlike, the pressure of the first reactor is 0.5MPa, and the temperature of the first reactor is 40 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.075 (mol/mol); The pressure of the second reactor is 0.5MPa, and the temperature of the second reactor is 40 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.024 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 0.01 (mol/mol).
Embodiment 17
The method identical with embodiment 13 is adopted to prepare propene polymer, unlike, the pressure of the first reactor is 4MPa, and the temperature of the first reactor is 90 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.082 (mol/mol); The pressure of the second reactor is 4MPa, and the temperature of the second reactor is 90 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.024 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 2 (mol/mol).
Embodiment 18
The method identical with embodiment 12 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and second, isobutyl dimethoxy silane is DT: DB=1: 1.
Embodiment 19
The method identical with embodiment 12 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and second, isobutyl dimethoxy silane is DT: DB=99: 1.
Comparative example 6
The method identical with embodiment 12 is adopted to prepare propene polymer, unlike, do not use second, isobutyl dimethoxy silane, the add-on of tetraethoxysilane makes Al/Si=20.
Comparative example 7
The method identical with embodiment 12 is adopted to prepare propene polymer, unlike, do not use tetraethoxysilane, the add-on of second, isobutyl dimethoxy silane makes Al/Si=20.
Embodiment 20
The method identical with embodiment 12 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and second, isobutyl dimethoxy silane is DT: DB=0.67: 1.
Embodiment 21
The method identical with embodiment 12 is adopted to prepare propene polymer, unlike, the mol ratio of tetraethoxysilane and second, isobutyl dimethoxy silane is DT: DB=199: 1.
Comparative example 8
The method identical with embodiment 13 is adopted to prepare propene polymer, unlike, replace second, isobutyl dimethoxy silane and tetraethoxysilane with dimethoxydiphenylsilane and four butoxy silanes, and the mol ratio of four butoxy silanes and dimethoxydiphenylsilane is 19: 1.
Comparative example 9
The method identical with embodiment 13 is adopted to prepare propene polymer, unlike, replace second, isobutyl dimethoxy silane and tetraethoxysilane with Cyclohexylmethyldimethoxysilane and tetramethoxy-silicane, and the mol ratio of tetramethoxy-silicane and Cyclohexylmethyldimethoxysilane is 19: 1.
Comparative example 10
The method identical with embodiment 13 is adopted to prepare propene polymer, unlike, in the first reactor, the embodiment of polyreaction is:
Tetraethoxysilane is sent into the first reactor from the first charging opening, second, isobutyl dimethoxy silane is sent into the first reactor from the second charging opening, wherein, first charging opening and second charging opening are arranged along the axis of reactor, be benchmark along the travel direction of material in described first reactor, the distance that first charging opening is positioned at the initiating terminal of described first reactor is 8% place of the total length of described first reactor, and described first charging opening is for adding tetraethoxysilane; The distance that described second charging opening is positioned at the initiating terminal of described first reactor is 75% of the total length of described first reactor, and described second charging opening is for adding second, isobutyl dimethoxy silane;
During polymerization, catalyst solid constituent and triethyl aluminum are sent into described first reactor from first charging opening respectively, and mixes with tetraethoxysilane, then pass into propylene and hydrogen from first charging opening, contact with said mixture and be polymerized; Be polymerized the mixture obtained then to contact with second, isobutyl dimethoxy silane, proceed polymerization, and remove unreacted propylene and hydrogen in mixture feeding tundish polymerization obtained.
Embodiment 22
Catalyst solid constituent prepared by preparation example 4 is added 50m continuously with 1.5g/h
3continuous horizontal type agitated bed Gas-phase reactor in, triethyl aluminum is added continuously with pump, the add-on of triethyl aluminum makes the mol ratio Al/Ti=800 of the aluminium in triethyl aluminum and the titanium in catalyst solid constituent, add tetraethoxysilane and second, isobutyl dimethoxy silane (both molar ratios are DT: DB=19: 1, the total amount mol ratio Al/Si=100 of the silicon in triethyl aluminum in the amount of aluminium and tetraethoxysilane and second, isobutyl dimethoxy silane) continuously.Then, in the first reactor, pass into propylene and hydrogen carries out polyreaction, wherein, the pressure of the first reactor is 1.6MPa, and the temperature of the first reactor is 90 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.095 (mol/mol), propylene and hydrogen mean residence time is in the reactor 40min.After the mixture exported by first reactor is sent into and is removed unreacted propylene and hydrogen in tundish, the product obtained is delivered to the second reactor, and ethene is passed in the second reactor, the pressure of the second reactor is 1.5MPa, the temperature of the second reactor is 90 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.026 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 0.12 (mol/mol), mean residence time is 40min.
Table 2 lists the test result of embodiment 11-22 and comparative example 6-10.
Table 2
*: four butoxy silanes/dimethoxydiphenylsilane
*: tetramethoxy-silicane/Cyclohexylmethyldimethoxysilane
Embodiment 23
Catalyst solid constituent prepared by preparation example 3 is added 50m continuously with 1.5g/h
3continuous horizontal type agitated bed Gas-phase reactor in, triethyl aluminum is added continuously with pump, the add-on of triethyl aluminum makes the mol ratio Al/Ti=200 of the aluminium in triethyl aluminum and the titanium in catalyst solid constituent, add n-propyl Trimethoxy silane (DN) and second, isobutyl dimethoxy silane (both molar ratios are DN: DB=19: 1, the total amount mol ratio Al/Si=60 of the silicon in triethyl aluminum in the amount of aluminium and n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane) continuously.Then, in the first reactor, pass into propylene and hydrogen carries out polyreaction, wherein, the pressure of the first reactor is 2.1MPa, and the temperature of the first reactor is 75 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.095 (mol/mol), propylene and hydrogen mean residence time is in the reactor 40min.After the mixture exported by first reactor is sent into and is removed unreacted propylene and hydrogen in tundish, the product obtained is delivered to the second reactor, and ethene is passed in the second reactor, the pressure of the second reactor is 2.2MPa, the temperature of the second reactor is 80 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.026 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 0.15 (mol/mol), mean residence time is 40min.
Embodiment 24
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, the mol ratio of n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane is DN: DB=39: 1.
Embodiment 25
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, the mol ratio of n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane is DN: DB=12: 1.
Embodiment 26
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, the mol ratio of n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane is DN: DB=9: 1.
Embodiment 27
The method identical with embodiment 24 is adopted to prepare propene polymer, unlike, the pressure of the first reactor is 0.5MPa, and the temperature of the first reactor is 40 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.084 (mol/mol); The pressure of the second reactor is 0.5MPa, and the temperature of the second reactor is 40 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.026 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 0.01 (mol/mol).
Embodiment 28
The method identical with embodiment 24 is adopted to prepare propene polymer, unlike, the pressure of the first reactor is 4MPa, and the temperature of the first reactor is 90 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.1 (mol/mol); The pressure of the second reactor is 4MPa, and the temperature of the second reactor is 90 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.1 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 2 (mol/mol).
Embodiment 29
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, the mol ratio of n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane is DN: DB=1: 1.
Embodiment 30
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, the mol ratio of n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane is DN: DB=99: 1.
Comparative example 11
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, do not use second, isobutyl dimethoxy silane, the add-on of n-propyl Trimethoxy silane makes Al/Si=20.
Comparative example 12
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, do not use n-propyl Trimethoxy silane, the add-on of second, isobutyl dimethoxy silane makes Al/Si=20.
Comparative example 13
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, replace second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane with dimethoxydiphenylsilane and four butoxy silanes, and the mol ratio of four butoxy silanes and dimethoxydiphenylsilane is 19: 1.
Comparative example 14
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, replace second, isobutyl dimethoxy silane and n-propyl Trimethoxy silane with Cyclohexylmethyldimethoxysilane and tetramethoxy-silicane, and the mol ratio of tetramethoxy-silicane and Cyclohexylmethyldimethoxysilane is 19: 1.
Comparative example 15
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, in the first reactor, the embodiment of polyreaction is:
N-propyl Trimethoxy silane is sent into the first reactor from the first charging opening, second, isobutyl dimethoxy silane is sent into the first reactor from the second charging opening, wherein, first charging opening and second charging opening are arranged along the axis of reactor, be benchmark along the travel direction of material in described first reactor, the distance that first charging opening is positioned at the initiating terminal of described first reactor is 8% place of the total length of described first reactor, the distance that described second charging opening is positioned at the initiating terminal of described first reactor is 75% of the total length of described first reactor,
During polymerization, catalyst solid constituent and triethyl aluminum are sent into described first reactor from first charging opening respectively, and mix with n-propyl Trimethoxy silane, then pass into propylene and hydrogen from first charging opening, contact with said mixture and be polymerized; Be polymerized the mixture obtained then to contact with second, isobutyl dimethoxy silane, proceed polymerization, and remove unreacted propylene and hydrogen in mixture feeding tundish polymerization obtained.
Embodiment 31
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, the mol ratio of n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane is DN: DB=0.67: 1.
Embodiment 32
The method identical with embodiment 23 is adopted to prepare propene polymer, unlike, the mol ratio of n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane is DN: DB=199: 1.
Embodiment 33
Catalyst solid constituent prepared by preparation example 4 is added 50m continuously with 1.5g/h
3continuous horizontal type agitated bed Gas-phase reactor in, triethyl aluminum is added continuously with pump, the add-on of triethyl aluminum makes the mol ratio Al/Ti=400 of the aluminium in triethyl aluminum and the titanium in catalyst solid constituent, add n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane (both molar ratios are DN: DB=9: 1, the total amount mol ratio Al/Si=80 of the silicon in triethyl aluminum in the amount of aluminium and n-propyl Trimethoxy silane and second, isobutyl dimethoxy silane) continuously.Then, in the first reactor, pass into propylene and hydrogen carries out polyreaction, wherein, the pressure of the first reactor is 2.5MPa, and the temperature of the first reactor is 60 DEG C, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.082 (mol/mol), propylene and hydrogen mean residence time is in the reactor 40min.After the mixture exported by first reactor is sent into and is removed unreacted propylene and hydrogen in tundish, the product obtained is delivered to the second reactor, and ethene is passed in the second reactor, the pressure of the second reactor is 2.6MPa, the temperature of the second reactor is 65 DEG C, the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.018 (mol/mol), the ethylene/propene ratio (C in the second reactor
2/ C
3) be 0.3 (mol/mol), mean residence time is 40min.
Embodiment 34
The method identical with embodiment 33 is adopted to prepare propene polymer, unlike, the hydrogen in the first reactor/propylene ratio (H
2/ C
3) be 0.075 (mol/mol), the hydrogen in the second reactor/propylene ratio (H
2/ C
3) be 0.024 (mol/mol).
Table 3 lists the test result of embodiment 23-34 and comparative example 11-15.
Table 3
*: four butoxy silanes/dimethoxydiphenylsilane
*: tetramethoxy-silicane/Cyclohexylmethyldimethoxysilane
Table 1 shows to the result of table 3, adopts method of the present invention can obtain good balance between hydrogen response and polymerization efficiency, can have the propene polymer of high melt mass flow rate with the preparation of high polymerization efficiency.Meanwhile, prepared according to the methods of the invention propene polymer has high degree of isotacticity, can reach more than 95%.
Claims (13)
1. a preparation method for propene polymer, the method comprises:
Under the first alkene gas-phase polymerization condition, first part's propylene and first part hydrogen are carried out first and contacts, remove described first and contact unreacted monomer and hydrogen in the mixture obtained, obtain the first product of contact; And
Under the second alkene gas-phase polymerization condition, make described first product of contact carry out second with second section propylene, second section hydrogen and comonomer and contact, to obtain described propene polymer, described comonomer is for being selected from ethene, C
4-C
101-alkene and C
4-C
8diolefin in one or more alkene;
Wherein, described first contact is carried out under the existence of olefin polymerization catalyst system, described olefin polymerization catalyst system contains solid ingredient, external donor compound and organo-aluminium compound, described solid ingredient contains titanium, magnesium and internal electron donor compound, described external donor compound contains the first outer Donor compound and the second external donor compound, described first external donor compound is n-propyl Trimethoxy silane, and described second external donor compound is second, isobutyl dimethoxy silane.
2. method according to claim 1, wherein, the mol ratio of described first external donor compound and described second external donor compound is 1-199:1.
3. method according to claim 2, wherein, the mol ratio of described first external donor compound and described second external donor compound is 1-99:1.
4. method according to claim 3, wherein, the mol ratio of described first external donor compound and described second external donor compound is 9-39:1.
5. method according to claim 1, wherein, the mol ratio of the titanium in the aluminium in described organo-aluminium compound and described solid ingredient is 20-2000:1, and the mol ratio of silicon total in the aluminium in described organo-aluminium compound and described external donor compound is 1-100:1.
6. method according to claim 1, wherein, in described first contact, the mol ratio of described first part hydrogen and described first part propylene is 0.075-0.095:1; In described second contact, the mol ratio of described second section hydrogen and described second section propylene is 0.018-0.028:1.
7. the method according to claim 1 or 6, wherein, with the total amount of described propene polymer for benchmark, the massfraction of described first product of contact is 40-99.5%.
8. method according to claim 1, wherein, the mol ratio of described comonomer and described second section propylene is 0.01-2:1.
9. the method according to claim 1 or 8, wherein, described comonomer is ethene.
10. method according to claim 1, wherein, described first alkene gas-phase polymerization condition comprises: temperature is 40-90 DEG C, and pressure is 0.5-4MPa; Described second alkene gas-phase polymerization condition comprises: temperature is 40-90 DEG C, and pressure is 0.5-4MPa.
11. 1 kinds of propene polymers prepared by the method in claim 1-10 described in any one.
12. propene polymers according to claim 11, wherein, described propene polymer is the multipolymer of ethene and propylene, the melt mass flow rate of described propene polymer is 80-150 gram/10 minutes, and described melt mass flow rate measures according to the method specified in GB/T 3682-2000.
13. propene polymers according to claim 12, wherein, the degree of isotacticity of described propene polymer is 95-98%.
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| CN103834206A (en) * | 2014-03-26 | 2014-06-04 | 张家港市康旭聚合体有限公司 | Propene polymer |
| CN105585772B (en) * | 2014-10-21 | 2018-05-15 | 中国石油化工股份有限公司 | A kind of acrylic resin and its preparation method and application and automobile instrument plate material |
| CN105622808B (en) * | 2014-10-31 | 2018-06-15 | 中国石油化工股份有限公司 | A kind of production method of impact polypropylene |
| CN110294813A (en) * | 2019-06-25 | 2019-10-01 | 陕西延长中煤榆林能源化工有限公司 | A kind of gas-phase polymerization polypropylene production technology using Mixed electron donor |
| CN112717562A (en) * | 2019-10-29 | 2021-04-30 | 中国石油化工股份有限公司 | Method for reducing content of entrained light components in polymer powder and application of method |
| CN112745581B (en) * | 2019-10-30 | 2022-07-26 | 中国石油化工股份有限公司 | High-fluidity high-crystallization impact-resistant polypropylene material and preparation method thereof |
| CN114426596A (en) * | 2020-10-15 | 2022-05-03 | 中国石油化工股份有限公司 | Catalyst for olefin polymerization, application thereof, olefin polymerization method and polymer |
| CN114437264B (en) * | 2020-10-20 | 2024-03-26 | 中国石油化工股份有限公司 | Low-VOC low-odor polypropylene resin and preparation method and application thereof |
| CN112625156B (en) * | 2020-12-04 | 2022-10-21 | 朴蓝聚烯烃科技发展（上海）有限公司 | Polypropylene preparation method suitable for gas phase polymerization process |
| CN113214416B (en) * | 2021-04-20 | 2022-07-26 | 国家能源集团宁夏煤业有限责任公司 | Combined external electron donor, olefin polymerization catalyst and application thereof, and polyolefin and preparation method thereof |
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